1-(2-Chloro­benzyl)­pyridinium bis­(maleo­nitrile­di­thiol­ato)­nickelate(III)

In the title complex, (C₁₂H₁₁ClN)[Ni(C₄N₂S₂)₂], the most prominent structural feature is the completely segregated columnar stacks of anions and cations. The neighbouring anions within the anionic column are equally spaced, with a distance of 4.0917 (8) Å between the Ni atoms. Hence, the Ni³⁺ ions form an uniformly spaced magnetic chain along the direction of the anionic stacking column.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.013 Å
• R factor = 0.088
• wR factor = 0.199
• Data-to-parameter ratio = 15.9

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


 Alert Level B:



RINTA_01  Alert B The value of Rint is greater than 0.15
          Rint given   0.183


 Alert Level C:



PLAT_371  Alert C Long   C(sp2)-C(sp1) Bond  C1     -   C2       =       1.44 Ang.

PLAT_371  Alert C Long   C(sp2)-C(sp1) Bond  C3     -   C4       =       1.45 Ang.

PLAT_371  Alert C Long   C(sp2)-C(sp1) Bond  C7     -   C8       =       1.42 Ang.


 0 Alert Level A = Potentially serious problem

 1 Alert Level B = Potential problem

 3 Alert Level C = Please check

---

S1. Comment

In recent years many new effects have been found especially for low-dimensional spin systems (Caneschi et al., 2001; Wolf et al., 2002; Mitsumi et al., 2002; Lorenz et al., 2002). Our aim is to construct quasi-one-dimensional molecule-based magnetic materials formed by plate-like maleonitriledithiolene (mnt) anionic metal complexes [M(mnt)₂]⁻ (M is Ni³⁺, Pd³⁺ or Pt³⁺). The magnetic properties of these types of low-dimensional magnetic materials are associated with columnar crystallographic packing. Recently, we have developed a new class of [R-BzPy]⁺[Ni(mnt)₂]⁻ salts, using the [Ni(mnt)₂]⁻ anion and derivatives of benzylpyridinium ([R-BzPy]⁺) as building blocks to construct low-dimensional molecular solids. We have found that the topology and size of the [R-BzPy]⁺ ion, which is related to its molecular conformation, can be modulated by systematic variation of the substituents on the aromatic rings. Hence, the stacking pattern of these complexes can be finely tuned through controlling the molecular conformation of the [R–BzPy]⁺ ion. To test this idea, a series of complexes have been obtained, which exhibit magnetic diversity (Ren et al., 2002; Xie, Ren, Song, Zou & Meng, 2002; Xie, Ren, Song, Zhang et al., 2002; Xie et al., 2003). In order to obtain further information concerning the nature of the effects of the substituents on the stacking pattern of these classes of ion-pair complexes, we report here the crystal structure of the title compound, (I), which has columnar packing.

In the anion of (I), the Ni atom exhibits square-planar coordination geometry involving four S atoms. The five-membered nickel-containing rings are slightly puckered (Fig. 1), as has been found in other [M(mnt)₂]^n- structures (Plumlee et al., 1975). The average S—Ni—S bond angle within the five-membered ring is 92.58 (6)° and the average Ni—S bond distance is 2.142 (2) Å. This compares well with similar bond distances and angles found in [Ni(mnt)₂]⁻ complexes (Ren et al., 2001, 2002). The anion is nearly planar, however the CN groups bend somewhat away from the plane of the four S atoms. For example, the largest deviations from the plane defined by the four S atoms are 0.149 (6) and 0.212 (6) Å for atoms C8 and N4, respectively.

The cation adopts a Λ-shape conformation, similar to other complexes in these series. However, the dihedral angles between the aromic rings and the reference plane deviate considerabley from 90°. The pyridine ring and the C14/C15/N5 reference plane are inclined by 55.06 (44)°, and the benzene ring is twisted towards the reference plane with a dihedral angle of 75.04 (53)°. This is different from the case of 1-(4-X-benzyl)pyridinium derivatives (X = substitutent).

The most prominent structural features of complex (I) are the completely segregated stacking columns of the [Ni(mnt)₂]⁻ anions and 1-(2-chlorobenzyl)pyridinium cations. This is illustrated by the projection along the crystallographic b axis shown in Fig. 2. Reports of completely segregated stacked columns of [Ni(mnt)₂]⁻ anions are rare (Ren et al., 2001). The Ni1···Ni1ⁱ [symmetry code: (i) 1 − x, −1/2 + y, 3/2 − z] distances between neighbouring anions within the [Ni(mnt)₂]⁻ column are equal [4.0917 (8) Å]. Hence, the Ni³⁺ ions form a uniformly spaced magnetic chain along the direction of the anionic column (Fig. 3). In the magnetic chain the shortest S···S (S2···S3ⁱ) and Ni···S (Ni1···S3ⁱ) distances are 3.806 (2) and 3.507 (2) Å, respectively. The nearest Ni1···Ni1ⁱⁱ [symmetry code: (ii) −x, −1/2 + y, 3/2 − z] contact between the [Ni(mnt)₂]⁻ columns is 10.952 (2) Å, which is much longer than the Ni···Ni distance within the [Ni(mnt)₂]⁻ column. These results indicate that, compared with intracolumnar interactions, the Ni···Ni magnetic exchange interactions between columns may be neglected, so this complex is an ideal magnetic chain compound. Within the column of 1-(2-chlorobenzyl)pyridinium cations, no π–π- or Cl–π-stacking interactions are found, which exist in 1-(4-chlorobenzyl)pyridinium bis(maleonitriledithiolato)nickelate(III) (Ren et al., 2002).

S2. Experimental

Disodium maleonitriledithiolate (Na₂mnt) was prepared following the literature procedure (Davison, et al., 1967). 1-(2-Chlorobenzyl)pyridinium chloride was prepared, by reacting 2'-chloro-benzylchlorine with 1.5 equivalents of pyridine in acetone and refluxed for 4 h. The product, a white microcrystalline solid, was filtered off, washed with acetone and diethyl ether in turn. The yield was more than 85% after having been dried in vaccum. NiCl₂·6H₂O, Na₂mnt and 1-(2-chlorobenzyl)pyridinium chloride (equivalent molar ratio 1:2:2) were then combined in water. The precipitate formed was filtered off, washed with water and then dissolved in a little MeCN. Iodine (1 molar equivalent) was added to the solution with stirring at room temperature. Three times the resulting volume of MeOH was then added and the mixture allowed to stand overnight. The microcrystals which formed were filtered off, washed with MeOH and dried in vacuum. Crystals suitable for structure analysis were obtained by diffusing diethyl ether into a MeCN solution of (I).

S3. Refinement

It was impossible to obtain good quality crystals. This results in a rather high R_int value and the fact that the crystal did not diffract significantly beyond 40° in 2θ.

Computing details

Data collection: SMART (Siemens, 1996); cell refinement: SMART (Siemens, 1996); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Figures

	Fig. 1. The structure of complex (I), showing displacement ellipsoids at 30% probability level and the atom-numbering scheme.
	Fig. 2. Packing diagram showing the completely separated column stacking in the b direction.
	Fig. 3. A view of the uniformly spaced anionic chain.

(I)

Crystal data

(C12H11ClN)[Ni(C4N2S2)2]	F(000) = 1100
Mr = 543.74	Dx = 1.595 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 25 reflections
a = 11.1294 (14) Å	θ = 3.6–15.5°
b = 6.9653 (9) Å	µ = 1.36 mm^−1
c = 31.174 (4) Å	T = 293 K
β = 110.437 (4)°	Needle, black
V = 2264.5 (5) Å^3	0.20 × 0.15 × 0.10 mm
Z = 4

Data collection

Siemens CCD area detector diffractometer	4443 independent reflections
Radiation source: fine-focus sealed tube	2303 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.183
ω scans	θmax = 26.1°, θmin = 2.0°
Absorption correction: empirical (using intensity measurements) (North et al., 1984)	h = −13→9
Tmin = 0.770, Tmax = 0.864	k = −8→8
12114 measured reflections	l = −36→38

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.088	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.199	H-atom parameters constrained
S = 1.09	w = 1/[σ^2(Fo^2) + (0.0511P)^2] where P = (Fo^2 + 2Fc^2)/3
4443 reflections	(Δ/σ)max = 0.017
280 parameters	Δρmax = 0.72 e Å^−3
0 restraints	Δρmin = −0.66 e Å^−3

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Ni1	0.49071 (7)	0.92787 (11)	0.78315 (2)	0.0551 (3)
S1	0.43290 (16)	0.9114 (3)	0.84206 (5)	0.0694 (5)
S2	0.29260 (15)	0.9349 (3)	0.73990 (5)	0.0686 (5)
S3	0.55471 (16)	0.9265 (2)	0.72602 (5)	0.0626 (4)
S4	0.68955 (15)	0.9344 (3)	0.82425 (5)	0.0670 (5)
N1	0.5737 (7)	0.8848 (12)	0.9681 (2)	0.127 (3)
N2	0.9099 (9)	0.9361 (14)	0.9443 (2)	0.155 (4)
N3	0.0927 (8)	0.9390 (11)	0.6171 (2)	0.122 (3)
N4	0.4327 (6)	0.9152 (9)	0.60028 (18)	0.0888 (18)
N5	0.7362 (6)	0.8436 (11)	0.55657 (18)	0.0840 (18)
C1	0.5750 (7)	0.8979 (11)	0.9320 (2)	0.090 (2)
C2	0.5758 (7)	0.9138 (9)	0.88617 (19)	0.0668 (17)
C3	0.6884 (7)	0.9220 (9)	0.8791 (2)	0.077 (2)
C4	0.8128 (9)	0.9296 (12)	0.9152 (2)	0.098 (3)
C5	0.1822 (7)	0.9368 (11)	0.6480 (2)	0.081 (2)
C6	0.2980 (6)	0.9321 (9)	0.68601 (19)	0.0651 (17)
C7	0.4162 (7)	0.9292 (8)	0.6805 (2)	0.0612 (16)
C8	0.4246 (7)	0.9202 (9)	0.6360 (2)	0.0680 (18)
C9	0.8274 (7)	0.8036 (17)	0.5391 (3)	0.117 (3)
H9A	0.8742	0.6902	0.5466	0.141*
C10	0.8501 (11)	0.933 (3)	0.5100 (3)	0.150 (6)
H10A	0.9115	0.9068	0.4968	0.180*
C11	0.7827 (14)	1.102 (2)	0.5002 (4)	0.155 (6)
H11A	0.8023	1.1923	0.4818	0.186*
C12	0.6855 (11)	1.1388 (16)	0.5174 (3)	0.130 (4)
H12A	0.6359	1.2496	0.5099	0.156*
C13	0.6675 (10)	1.0012 (15)	0.5462 (3)	0.102 (3)
H13A	0.6040	1.0206	0.5587	0.122*
C14	0.7046 (6)	0.6963 (11)	0.5862 (2)	0.083 (2)
H14A	0.6390	0.7472	0.5969	0.099*
H14B	0.6702	0.5828	0.5680	0.099*
C15	0.8185 (6)	0.6417 (12)	0.6262 (2)	0.0707 (18)
C16	0.8674 (7)	0.7597 (11)	0.6640 (2)	0.080 (2)
C17	0.9709 (7)	0.7081 (15)	0.7006 (2)	0.092 (2)
H17A	1.0023	0.7910	0.7254	0.111*
C18	1.0284 (8)	0.5376 (17)	0.7012 (3)	0.102 (3)
H18A	1.1000	0.5048	0.7264	0.122*
C19	0.9834 (9)	0.4119 (14)	0.6655 (4)	0.113 (3)
H19A	1.0214	0.2923	0.6664	0.135*
C20	0.8801 (9)	0.4675 (14)	0.6280 (3)	0.101 (3)
H20A	0.8506	0.3851	0.6030	0.121*
Cl1	0.7937 (2)	0.9798 (3)	0.66419 (6)	0.1007 (7)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ni1	0.0585 (5)	0.0587 (5)	0.0465 (4)	−0.0016 (4)	0.0164 (3)	−0.0026 (3)
S1	0.0694 (10)	0.0883 (13)	0.0528 (9)	0.0114 (9)	0.0241 (8)	0.0000 (8)
S2	0.0548 (9)	0.0906 (13)	0.0569 (9)	−0.0054 (9)	0.0150 (7)	−0.0009 (8)
S3	0.0636 (9)	0.0733 (11)	0.0507 (8)	−0.0042 (8)	0.0196 (7)	−0.0019 (8)
S4	0.0583 (9)	0.0845 (13)	0.0524 (9)	−0.0006 (8)	0.0121 (7)	−0.0042 (8)
N1	0.128 (6)	0.203 (8)	0.051 (4)	0.064 (6)	0.034 (4)	0.015 (4)
N2	0.132 (7)	0.238 (11)	0.062 (4)	0.004 (7)	−0.007 (5)	−0.026 (5)
N3	0.097 (5)	0.160 (8)	0.077 (4)	−0.024 (5)	−0.009 (4)	0.007 (4)
N4	0.114 (5)	0.098 (5)	0.048 (3)	−0.011 (4)	0.021 (3)	−0.003 (3)
N5	0.070 (4)	0.115 (6)	0.055 (3)	−0.037 (4)	0.007 (3)	−0.011 (4)
C1	0.089 (5)	0.116 (7)	0.062 (5)	0.050 (5)	0.023 (4)	0.006 (4)
C2	0.077 (4)	0.074 (5)	0.049 (3)	0.020 (4)	0.021 (3)	−0.005 (3)
C3	0.084 (5)	0.081 (5)	0.051 (4)	0.012 (4)	0.004 (3)	−0.013 (3)
C4	0.106 (6)	0.118 (7)	0.053 (4)	0.020 (5)	0.008 (4)	−0.015 (4)
C5	0.072 (4)	0.101 (6)	0.054 (4)	−0.016 (4)	0.002 (4)	0.007 (4)
C6	0.071 (4)	0.066 (4)	0.049 (3)	−0.014 (3)	0.008 (3)	−0.004 (3)
C7	0.083 (4)	0.048 (4)	0.052 (3)	−0.013 (3)	0.024 (3)	0.002 (3)
C8	0.089 (5)	0.060 (4)	0.048 (4)	−0.014 (4)	0.016 (3)	−0.006 (3)
C9	0.077 (5)	0.192 (10)	0.087 (5)	−0.030 (6)	0.033 (5)	0.004 (6)
C10	0.094 (7)	0.285 (18)	0.070 (6)	−0.073 (9)	0.028 (5)	0.001 (8)
C11	0.132 (10)	0.228 (16)	0.077 (7)	−0.062 (10)	0.001 (7)	0.045 (8)
C12	0.154 (9)	0.158 (9)	0.052 (5)	−0.055 (8)	0.004 (5)	0.005 (5)
C13	0.114 (7)	0.125 (8)	0.063 (5)	−0.041 (6)	0.026 (5)	−0.016 (5)
C14	0.079 (5)	0.101 (6)	0.067 (4)	−0.042 (4)	0.024 (4)	−0.011 (4)
C15	0.059 (4)	0.089 (5)	0.069 (4)	−0.017 (4)	0.028 (3)	−0.005 (4)
C16	0.073 (4)	0.100 (6)	0.074 (5)	−0.019 (4)	0.037 (4)	−0.008 (4)
C17	0.077 (5)	0.133 (8)	0.061 (4)	−0.002 (5)	0.017 (4)	0.004 (5)
C18	0.066 (5)	0.147 (9)	0.085 (6)	−0.006 (6)	0.018 (4)	0.027 (6)
C19	0.080 (6)	0.116 (8)	0.149 (9)	−0.012 (6)	0.049 (6)	0.006 (7)
C20	0.087 (6)	0.116 (8)	0.099 (6)	−0.032 (6)	0.032 (5)	−0.029 (5)
Cl1	0.1131 (15)	0.1066 (16)	0.0794 (12)	−0.0027 (13)	0.0298 (11)	−0.0174 (11)

Geometric parameters (Å, º)

Ni1—S3	2.1367 (16)	C9—H9A	0.9300
Ni1—S4	2.1356 (17)	C10—C11	1.369 (16)
Ni1—S2	2.1460 (17)	C10—H10A	0.9300
Ni1—S1	2.1505 (16)	C11—C12	1.388 (16)
S1—C2	1.701 (7)	C11—H11A	0.9300
S2—C6	1.702 (6)	C12—C13	1.374 (11)
S3—C7	1.691 (7)	C12—H12A	0.9300
S4—C3	1.716 (7)	C13—H13A	0.9300
N1—C1	1.134 (8)	C14—C15	1.485 (9)
N2—C4	1.144 (10)	C14—H14A	0.9700
N3—C5	1.117 (8)	C14—H14B	0.9700
N4—C8	1.147 (7)	C15—C20	1.385 (11)
N5—C13	1.313 (11)	C15—C16	1.383 (9)
N5—C9	1.337 (9)	C16—C17	1.357 (9)
N5—C14	1.502 (8)	C16—Cl1	1.740 (8)
C1—C2	1.437 (9)	C17—C18	1.346 (11)
C2—C3	1.349 (9)	C17—H17A	0.9300
C3—C4	1.448 (10)	C18—C19	1.368 (12)
C5—C6	1.414 (9)	C18—H18A	0.9300
C6—C7	1.385 (9)	C19—C20	1.378 (12)
C7—C8	1.426 (8)	C19—H19A	0.9300
C9—C10	1.364 (14)	C20—H20A	0.9300
S3—Ni1—S4	85.58 (6)	C11—C10—H10A	120.0
S3—Ni1—S2	92.57 (6)	C10—C11—C12	120.9 (12)
S4—Ni1—S2	176.87 (7)	C10—C11—H11A	119.5
S3—Ni1—S1	176.18 (7)	C12—C11—H11A	119.5
S4—Ni1—S1	92.59 (7)	C13—C12—C11	115.6 (12)
S2—Ni1—S1	89.41 (7)	C13—C12—H12A	122.2
C2—S1—Ni1	102.5 (2)	C11—C12—H12A	122.2
C6—S2—Ni1	103.7 (2)	N5—C13—C12	122.6 (10)
C7—S3—Ni1	103.2 (2)	N5—C13—H13A	118.7
C3—S4—Ni1	103.3 (3)	C12—C13—H13A	118.7
C13—N5—C9	122.3 (8)	C15—C14—N5	112.1 (5)
C13—N5—C14	118.8 (7)	C15—C14—H14A	109.2
C9—N5—C14	118.8 (8)	N5—C14—H14A	109.2
N1—C1—C2	179.6 (10)	C15—C14—H14B	109.2
C3—C2—C1	119.7 (6)	N5—C14—H14B	109.2
C3—C2—S1	121.9 (5)	H14A—C14—H14B	107.9
C1—C2—S1	118.4 (5)	C20—C15—C16	116.4 (7)
C2—C3—C4	124.4 (6)	C20—C15—C14	121.5 (7)
C2—C3—S4	119.7 (5)	C16—C15—C14	122.0 (7)
C4—C3—S4	115.8 (6)	C17—C16—C15	121.7 (8)
N2—C4—C3	178.7 (9)	C17—C16—Cl1	119.6 (6)
N3—C5—C6	178.1 (9)	C15—C16—Cl1	118.8 (6)
C7—C6—C5	121.5 (6)	C16—C17—C18	120.4 (8)
C7—C6—S2	119.0 (5)	C16—C17—H17A	119.8
C5—C6—S2	119.4 (5)	C18—C17—H17A	119.8
C6—C7—C8	120.6 (6)	C17—C18—C19	121.1 (8)
C6—C7—S3	121.5 (5)	C17—C18—H18A	119.4
C8—C7—S3	117.8 (5)	C19—C18—H18A	119.5
N4—C8—C7	178.9 (7)	C18—C19—C20	118.1 (9)
N5—C9—C10	118.4 (11)	C18—C19—H19A	121.0
N5—C9—H9A	120.8	C20—C19—H19A	121.0
C10—C9—H9A	120.8	C15—C20—C19	122.3 (8)
C9—C10—C11	120.1 (12)	C15—C20—H20A	118.8
C9—C10—H10A	120.0	C19—C20—H20A	118.9